Nitrogen coordinated silicon compounds



United States Patent 3,1331% NETRQSEN CGORDENATED SELHJUN CGMPSUNDS Arnold B. Finestone, West Newton, Masa, assignor to 3,133,108 Patented May 12, 1%64 sisting of the hydrogen radical, alkyl radicals, cyoloalkyl radicals and aryl radicals.

Table II below sets forth examples of some of the alkanolamines that may be employed in carrying out Westinghouse Electric tlorporation, East Pittsburgh, 5 fins mventlonV 11 i i 1 9 i s s N 751 632 TABLE H o rat-vin Fl e u v 2 oer. o.

4 Claims. "cries-i482 Alkanolammes This invention relates to certain nitrogen coordinated 10 M0110 silicon compounds and to their method of preparation. g

t e oi this inveiiioi is t provide niimei anaraaaar--- attenuates-e11: httitttaft ordinated silicon compounds resulting from the reaction amine. amine. of alkanolamines and certain organosilicon compounds. ggggg g g fi Another object of this invention is to provide a method 15 N, N-diphenyl N-ethyldiethanob of producing nitrogen coordinated silicon compounds by fihgfififiifif gtg m diethanoL the reaction of alkanolamines and certain organos-ihcon isopropanolamine. Nfirl'riilgiligddiiso compounds.

Other objects of this invention will, in part, be obvious propanolamme' and Will, in part, appear hereinafter. For a better under- I standing of the nature and objects of this invention, ref- Z 2 23 igg g ftg i fiifi g 180p mp anol erence should be had to the following detailed description. p y OH Broadly, in the attainment of the foregoing objects and in accordance with this invention, there is provided a H process for preparing certain nitrogen coordinated sili- 25 wherein X is O, 1 2 and Y is 2 and 1lhe tohal con compounds which comprises admixing an alkano-l-aof X and Y R" y he y g radical; y mine and a pantially or completely esterified organosiliradicals including, for p y fithyl, P PY and con compound, heating the admixture to reflux, refluxing P PY of y radicals including, for example, P YL the admixture until a predetermined amount of monomethyl P y and chlohophehyl- Rm Inlay b6 the Y hydric alcohol is removed, and recovering the nitrogen 3O 8 radical the y coordinated silicon compound. The monohydric alcohol In carrying out Process of this invention, there are that is removed is one of the products of the reaction, and reacted from one 11101 0' W0 1018 f h a amin the nitrogen coordinated silicon compound that is subseand 0116 H101 of the orgah'osilicoh mp In P quently recovered is the other reaction product. It has lice, however, it is desirable, in Order Produce Seleched been found that the nitrogen coordinated silicon 'comcompounds, that either Precisely one "1101 111015 of pound prepared in accordance with this invention may alkaholamihe be employed for each n101 of the Ofghhocomprise the monomer or a low molecular weight poly- Silicon p Y excess of alkaholamihe p y mer yfihereof, such, for example, as the di ner or rtpimen abOV'E TWO H1018 only necessitate its removal after the The Organosflicon icompgunds employed in {his inven- IeaCDiOTl is completed. AS be noted in the specific tion are those that have the formula 40 examples that follow, diiterent compounds will resnit de- (R) pending upon the molar ratio of reactants employed.

11 m The desired amount of reactants is placed in a suitwherein n is 0, 1, 2 or 3 and m is 1, 2, 3 or 4; and the able reaction vessel where they are thoroughly admixed total of n and m is 4. R and R may be alkyl radicals and heated to reflux. Reflux is continued until a predeterincluding, for example, methyl, ethyl, propyl, isopropyl, mined amount of monohydric alcohol, one of the prodbutyl and isobutyl; or aryl radicals including, for exnets of the reaction, is removed. The nitrogen coordiample, phenyl, benzyl, methyl phenyl and chlorophenyl. nated silicon reaction product is then recovered. The

Table I below lists several specific examples of organonitrogen coordinated silicon compound will be a crystalsilicon compounds that may be employed in carrying out line solid or a liquid depending on the reactants eminvention. It will be noted that these examples fall ployed. The crystalline solid compound may be puri- Within the above formula and they are grouped under fied by recrystallization from a solvent or by other conthe various values that have been given to n and m above. ventional means, if desired.

TABLE I Organosilicon Compounds Having the Formula )n- ')m n =0 n =1 11 2 n =3 m =4 m=3 m=2 m=1 methyl orthosilicate methyltrietlioxysilane dimethyldirnethoxysilane triethylethoxysilane ethyl orthosilicate ethyltriethoxysilane dimethyldiethoxysilane trimethyethoxysilane propyl orthosilicate propyltriethoxysilane diethyldiethoxysilane triethylphenoxysilane Zethylbutyl ortliosilicate ethyltrimethoxysilane methylphenyldiethoxysilane trimethylmetlioxysilane phonyltriethosysilane diphenyldiethoxysilane methylethyldiethoxysilane diethyldiphenoxysilane When the reactants are reacted on a 1:1 molar basis it has been found desirable to employ in admixture with the reactants at least 5% by weight, based on the total weight of the reactants, of an inert solvent that will form an azeotropic mixture with the monohydric alcohol reaction product to insure adequate removal of the monohydr'ic alcohol. Examples of suitable azeotropisers that may be employed are benzene, toluene and xylene. Any azeotropiser remaining in the reaction vessel after the reaction has been completed may be removed by heating under reduced pressure. v

In order to produce a strong coordinate bond between the nitrogen and silicon when the reactants are reacted on a 1:1 molar basis, it is deisrable to continue refluxing the reactants until all the monohydric alcohol reaction product capable of being formed by the reaction has been removed. V

In carrying out the reaction employing two mols of alkanolamine and one mol of organosilicon compound, it is only necessary to proceed with the reaction until at least two mols of the alcohol reaction product are re moved. In some cases, the natureof the reactants is such that it is possible to produce more than two mols of the monohydric alcohol reaction product, and the reaction may be further carried out to accomplish this removal.

To illustrate more fully this point, the following example is set forth.

EXAMPLE I CHiCH2NCHi-CH2OH The refluxing may, however, be continued to remove a total of either three mols or four mols of ethanol,

and two other reaction products will result. These two products have the following structural formulas III i CHr-CHr-NeCHr-CH;

Triethanolamine 74.5 grams (0.5 mol). Phenyltriethoxysilane grams (0.5 mol).

, Benzene (azeotropiser) 500 milliliters.

The reactants are admixed thoroughly and heated slowly to reflux. Reflux is continued until substantially all the ethanol, one of the reaction products, is removed by azeotropic distillation. The reaction product remaining in the flask is dissolved in hot benzene and recrystallized therefrom. The recrystallized compound, phenyltriethanolaminesilane, is a white crystalline solid having a melting point of 203.6 C. to 204.2 C. This compound has a strong nitrogen to silicon coordinate bond. This compound has been determined to have the structural formula EXAMPLE III The following ingredients are reacted in apparatus similar to that described in Example 1.

grams (1 mol). grams (1 mol). milliliters.

Triethanolamine 149 Methyltriethoxysilane 178 Benzene (Azeotropiser) 400 The reactants are thoroughly admixed and heated slowly to reflux. Reflux is continued until substantially all the ethanol, one of the reaction products, is removed by azeotropic distillation. The reaction product remaining in the flask is dissolved in warm benzene and recrystallized. The recrystallized product, methyltriethanolaminesilane, has a melting point of from 139.5 C. to 142 C. This compound may further be purified by sublimation at 60 C./O.8 mm. The structural formula for EXAMPLE IV 'The following ingredients are reacted in apparatus similar to that used in Example I;

Triethanolamine 149 grams (1 mol). Ethyl orthosilicate 208 grams (1 mol). Benzene (Azeotropiser) 400 milliliters.

EXAMPLE V The following ingredients are reacted in apparatus similar to that employed in Example I.

Triethanolamine 298 grams (2 mols). Ethyl orthosilicate 208 grams (1 mol).

The reactants are thoroughly admixed and heated slowly to reflux. Reflux is continued until four mole of ethanol are distilled off. The reaction product remaining in the flask is a liquid. This reaction product has the structural formula CHg-CH -OH OHg-CH -OH EXAMPLE VI Employing the apparatus of Example I, the following ingredients are reacted: N-methyldiethanolamine 119 grams (1 mol). Ethyl orthosilicate 104 grams (0.5 mol).

The ingredients are thoroughly admixed and heated slowly to reflux. Reflux is continued until 2 mols of ethanol are removed. The reaction product remaining in the flask is a liquid and has the structural formula The following ingredients are charged into a threeneck, one-half liter flask with attachments employed in Example I:

N-methyldiethanolarnine 60 grams (0.5 mol). Diethoxy methylphenylsilane 105 grams (0.5 mol).

The reactants are heated slowly to reflux and refluxed until 1 mol of ethanol is removed. The reaction product remaining in the flask is a liquid and has the structural formula The following ingredients are charged into a threeneck, one liter flask fitted with attachments similar to those employed in Example I:

Diisopropanolamine 133.19 grams (1 mol). Diethoxymethylphenyl silane 210 grams (1 mol).

The ingredients are admixed and heated slowly to reflux. Reflux is continued until two mols of isopropanol are removed. The reaction product remaining in the flask is a liquid and has the structural formula EXAMPLE IX The following ingredients are charged into a threeneck, one-half liter flask with attachments employed in Example I:

Ethyl orthosilicate 268 grams (1 mol). N-methyldiethanolamine grams (1 mol).

The reactants are heated slowly to reflux and refluxed until 2 mols of ethanol are removed. The reaction prodnot has the structural formula The nitrogen coordinated silicon compounds of this invention may be employed as curing catalysts for epoxy resins and as intermediates for the preparation of other compounds. Thus, 8 parts by weight of the nitrogen coordinated silicon compound of Example VII is added to about 75 parts by weight of an epoxy resin and cured to a thermoset state in about 4 hours when heated to a temperature of about C.

It will be understood that the above examples and description are illustrative and not in limitation of the invention. V

I claim as my invention: 1

1. A nitrogen coordinated silicon compound having the formula 2. A nitrogen coordinated silicon compound having the formula 3. A nitrogen coordinated silicon'compound having the formula 4. A nitrogen coordinated silicon compound having the formula I V o ;oHi N-o11'.- -orn CH No references cited. 

1. A NITROGEN COORDINATED SILICON COMPOUND HAVING THE FORMULA
 2. A NITROGEN COORDINATED SILICON COMPOUND HAVING THE FORMULA
 3. A NITROGEN COORDINATED SILICON COMPOUND HAVING THE FORMULA
 4. A NITROGEN COORDINATED SILICON COMPOUND HAVING THE FORMULA 